Ink jet ink

ABSTRACT

The present invention pertains to an aqueous inkjet ink made from certain aqueous titanium dioxide slurries, and an associated inkjet ink set for inkjet printing. The invention also pertains to a method of inkjet printing with the ink and ink set. The use of the specific titanium dioxide slurries described herein result in inkjet inks having improved stability and better anti-settling performance with less pigment agglomeration and flocculation over time.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention pertains to an aqueous inkjet ink made fromcertain titanium dioxide slurries and an associated inkjet ink set forinkjet printing. The invention also pertains to a method of inkjetprinting with the ink and ink set. The use of the specific titaniumdioxide slurries described herein result in inkjet inks having improvedstability and better anti-settling performance with less pigmentagglomeration and flocculation over time.

2. Description of the Related Art

Inkjet printing is a non-impact printing process in which droplets ofink are deposited on print media, such as paper or polymeric substrates,to form the desired image. The droplets are ejected from a printhead inresponse to electrical signals generated by a microprocessor.

Colored inkjet inks comprise one or more colorants that are dissolved(e.g., dyes) and/or dispersed (e.g., pigments and dispersed dyes) in theink vehicle. The ink vehicle can be aqueous (a significant amount ofwater) or non-aqueous (predominantly organic liquid), and the ink isreferred to as aqueous or non-aqueous ink accordingly.

Aqueous ink is advantageous because water is especially environmentallyfriendly. There are many applications, though, where aqueous ink istypically unsuitable and non-aqueous ink must be used. Many, if not mostof these non-aqueous ink applications involve printed articles onhydrophobic substrates, and particularly printed articles on polymersubstrates, which will be exposed to sunlight, and the preferredcolorants in these applications are pigments because of their well-knowadvantage in fade resistance compared to dyes.

Dispersion of pigments in a non-aqueous vehicle is substantiallydifferent than dispersion in an aqueous vehicle. Generally, pigmentsthat can be dispersed well in water do not disperse well in non-aqueoussolvent, and vice versa.

Also, the demands of inkjet printing are quite rigorous and thestandards of dispersion quality are high. Thus, pigments that may be“well dispersed” for other applications are often still inadequatelydispersed for inkjet applications.

There is a need for improved pigment selection especially for a stableaqueous ink for inkjet inks. In particular, there is a need for whitepigments that can be sufficiently stabilized in inkjet compatibleformulations so that the resultant ink can be effectively jetted, evenafter being stored or otherwise unused for some period of time. Inaddition the ability to use an ink containing a white pigment tocomplement other inks of an ink set can lead to improved images,especially when lighter tones and/or higher degrees of coverage oropacity are needed.

White inks are useful and provide good visibility when printed ontransparent and colored surfaces. White printing on these surfaces isdesirable in numerous end uses, such as the computer industry (printedcircuit boards, computer chips), recording industry (tapes, film, etc.),packaging and automotive coatings. White ink may be used not only todetail and add decals to automobiles, but also to other motor vehicles,including trucks, planes and trains, as well as bicycles, etc. White inkmay also be useful on other surfaces, such as plastics, wood, metal,glass, textiles, polymeric films and leather for both practical andornamental purposes.

White ink formulations typically contain a particulate white pigmentdispersed in a solvent (aqueous or non-aqueous)/resin system. Currentwhite ink formulations are not acceptable for numerous applications,such as commercial inkjet applications, primarily because of poorstability resulting in pigment settling and agglomeration. Poorstability may result in “nozzle outs” or plugging of the ink jetnozzles. For example, a typical print head on an industrial printer has256 nozzles, each nozzle head having a diameter of about 50 microns insize. Large pigment particles and agglomerates may plug the nozzles.Poor stability also results in poor hiding, non-uniform coverage andpoor clarity in the printed surface.

White ink formulations based on inorganic white pigments, such astitanium dioxide (TiO₂), may fail because of poor stabilization of theTiO₂ pigment. Pigment agglomeration and flocculation are often at faultin poor performance of white inks, particularly white inkjet inks, dueto settling and nozzle plugging problems.

As a result, there is a need for an ink formulation containing a whitepigment for use in ink and inkjet systems that avoid the aforementionednegative attributes. There is further a need for a titanium dioxideslurry that does not suffer from stability problems when incorporatedinto ink formulations. There is still a further need for an aqueoussystem that includes all these benefits. The present invention meetsthese needs.

SUMMARY OF THE INVENTION

In one aspect of the present invention, there is provided an aqueousinkjet ink comprising an aqueous vehicle having dispersed therein:

-   (a) a titanium dioxide pigment;-   (b) a combination of dispersants comprising:    -   (1) a graft copolymer having a weight average molecular weight        of from about 4000 to about 100000, comprising from about 90% to        about 50% by weight of a polymeric backbone, and from about 10%        to about 50% by weight of macromonomer side chains attached to        the backbone, the polymeric backbone and macromonomer side        chains comprising 100 wt % of the graft copolymer, wherein:        -   (i) the polymeric backbone is hydrophobic in comparison to            the macromonomer side chains and comprises one or more            polymerized ethylenically unsaturated hydrophobic monomers            and, optionally, up to about 20% by weight, based on the            weight of the graft copolymer, of polymerized ethylenically            unsaturated acid monomers; and        -   (ii) each of the macromonomer side chains individually is a            hydrophilic polymer containing acids groups attached to the            polymeric backbone at a single terminal point, and            -   (A) has a weight average molecular weight of from about                1000 to about 30000, and            -   (B) comprises from about 2% to about 100% by weight,                based on the weight of the macromonomer side chain, of a                polymerized ethylenically unsaturated acid monomer, and            -   (C) wherein the acid groups are at least partially                neutralized, preferably with an inorganic base and/or an                amine;    -   (2) a block copolymer of type AB, ABA or ABC wherein at least        one of the blocks in the block copolymer is an adsorbing        segment, and wherein at least one of the blocks in the block        copolymer is a stabilizing segment.

In another aspect of the present invention, there is provided an aqueousinkjet ink comprising a vehicle to which has been added an aqueoustitanium dioxide slurry comprising:

-   (a) a titanium dioxide pigment; and-   (b) a combination of dispersants comprising:    -   (1) a graft copolymer having a weight average molecular weight        of from about 4000 to about 100000, comprising from about 90% to        about 50% by weight of a polymeric backbone, and from about 10%        to about 50% by weight of macromonomer side chains attached to        the backbone, the polymeric backbone and macromonomer side        chains comprising 100 wt % of the graft copolymer, wherein:        -   (i) the polymeric backbone is hydrophobic in comparison to            the macromonomer side chains and comprises polymerized            ethylenically unsaturated hydrophobic monomers and,            optionally, up to about 20% by weight, based on the weight            of the graft copolymer, of polymerized ethylenically            unsaturated acid monomers; and        -   (ii) each of the macromonomer side chains individually is a            hydrophilic polymer containing acids groups attached to the            polymeric backbone at a single terminal point, and            -   (A) has a weight average molecular weight of from about                1000 to about 30000, and            -   (B) comprises from about 2% to about 100% by weight,                based on the weight of the macromonomer side chain, of a                polymerized ethylenically unsaturated acid monomer, and            -   (C) wherein the acid groups are at least partially                neutralized with an inorganic base or an amine;    -   (2) a block copolymer of type AB, ABA or ABC wherein at least        one of the blocks in the block copolymer is an adsorbing        segment, and wherein at least one of the blocks in the block        copolymer is a stabilizing segment; and-   (c) a liquid carrier.

By an “aqueous inkjet ink” is meant an inkjet ink with a water contentof greater than about 10 wt %, and preferably greater than about 25 wt%, based on the total ink weight.

These inkjet inks may further comprise a variety of optional additivesof a general type known to those of ordinary skill in the art, as partof the titanium dioxide slurry and/or added to the inkjet ink separatelytherefrom. Such optional additives include, for example, otherdispersants, humectants and rheology modifiers.

In one specific preferred embodiment, the inkjet ink further comprises,as a third dispersant, a phosphated acrylic copolymer, different fromthe graft copolymer (1) or block copolymer (2), comprising a hydrophilicstabilizing segment and a hydrophobic adsorbing segment. This thirddispersant is preferably part of the titanium oxide slurry, but can alsobe added separately therefrom.

Advantageously, by use of the graft copolymer dispersant in combinationwith the block copolymer dispersant as listed above, an aqueous inkjetink can be formulated in which settling of titanium dioxide particles isreduced. A further advantageous reduction in settling of particles isachieved using a blend of the graft copolymer dispersant, the blockcopolymer dispersant, and the phosphated acrylic copolymer as listedabove. Moreover, even when settling does occur, the settling is “soft”settling, meaning the titanium dioxide pigment can be readilyre-dispersed and rejuvenated by low shear mixing so as not to result inplugging of inkjet printhead nozzles. Low shear mixing includes, forexample, simple shaking (e.g., by hand or movement of the inkjetprinthead) or stirring with an impeller or mixing blades at speeds ofless than about 500 rpm wherein no grinding occurs. In contrast, “hard”settling occurs with many titanium dioxide slurries of the prior art.

The titanium dioxide pigment used herein is white, thus the inkjet inksof the present invention are preferably white. Non-white colored inkscan also be made by utilizing one or more additional colorants in theink.

In accordance with another aspect of the present invention, there isprovided an inkjet ink set comprising a plurality of colored, pigmentedinks, at least one of which is an aqueous inkjet ink (and preferably awhite inkjet ink) as set forth above.

The aqueous inkjet inks of the present invention are suitable, forexample, for use in personal, business and industrial inkjet printers,and numerous other printing applications. Furthermore, they can be usedfor printing a wide variety of substrates including non-white paper,transparencies, polymer substrates, textiles, etc.

The present invention thus also provides a method for inkjet printingonto a substrate, comprising the steps of:

-   -   (1) providing an inkjet printer that is responsive to digital        data signals;    -   (2) loading the printer with a substrate to be printed;    -   (3) loading the printer with the above-mentioned inkjet ink or        inkjet ink set; and    -   (4) printing onto the substrate using the inkjet ink set in        response to the digital data signals.

These and other features and advantages of the present invention will bemore readily understood by those of ordinary skill in the art from areading of the following detailed description. It is to be appreciatedthat certain features of the invention which are, for clarity, describedabove and below in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures of the invention that are, for brevity, described in thecontext of a single embodiment, may also be provided separately or inany subcombination. In addition, references in the singular may alsoinclude the plural (for example, “a” and “an” may refer to one, or oneor more) unless the context specifically states otherwise. Further,reference to values stated in ranges include each and every value withinthat range.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides an aqueous ink, preferably an aqueouswhite ink, that is preferably made from a particularly titanium dioxideslurry. The titanium dioxide slurry and ink made therefrom have improvedstability to agglomeration upon storage. The titanium dioxide slurry andink utilize specific mixtures of dispersants in amounts to stabilize andkeep the pigments deflocculated over extended periods of time both inslurry form and when the slurry is subsequently used in an inkformulation. As a result, the ultimate ink formulation providesdesirable properties such as good hiding, uniform coverage, and goodclarity when applied to surfaces.

Titanium Dioxide Pigment

Titanium dioxide (TiO₂) pigment useful in the present invention may bein the rutile or anatase crystalline form. It is commonly made by eithera chloride process or a sulfate process. In the chloride process, TiCl₄is oxidized to TiO₂ particles. In the sulfate process, sulfuric acid andore containing titanium are dissolved, and the resulting solution goesthrough a series of steps to yield TiO₂. Both the sulfate and chlorideprocesses are described in greater detail in “The Pigment Handbook”,Vol. 1, 2nd Ed., John Wiley & Sons, NY (1988), the relevant disclosureof which is incorporated by reference herein for all purposes as iffully set forth.

The titanium dioxide particles can have a wide variety of averageparticle sizes of about 1 micron or less, depending on the desired enduse application of the ink.

The titanium dioxide pigment is in and of itself white in color.

For applications demanding high hiding or decorative printingapplications, the titanium dioxide particles preferably have an averagesize of less than about 1 micron (1000 nanometers). Preferably, theparticles have an average size of from about 50 to about 950 nanometers,more preferably from about 75 to about 750 nanometers, and still morepreferably from about 100 to about 500 nanometers. These titaniumdioxide particles are commonly called pigmentary TiO₂.

For applications demanding white color with some degree of transparency,the pigment preference is “nano” titanium dioxide. “Nano” titaniumdioxide particles typically have an average size ranging from about 10to about 200 nanometers, preferably from about 20 to about 150nanometers, and more preferably from about 35 to about 75 nanometers. Anink comprising nano titanium dioxide can provide improved chroma andtransparency, while still retaining good resistance to light fade andappropriate hue angle. A commercially available example of an uncoatednano grade of titanium oxide is P-25, available from Degussa (ParsippanyN.J.).

In addition, unique advantages may be realized with multiple particlesizes, such as opaqueness and UV protection. These multiple sizes can beachieved by adding both a pigmentary and a nano grade of TiO₂.

The titanium dioxide is preferably incorporated into an ink formulationvia a slurry concentrate composition. The amount of titanium dioxidepresent in the slurry composition is preferably from about 15 wt % toabout 80 wt %, based on the total slurry weight.

For slurries wherein the majority of titanium dioxide particles are of apigmentary size, and preferably those in which the average particle sizeis greater than about 200 nanometers up to about 1 micron, the amount oftitanium dioxide in the slurry is preferably from about 50 wt % to about75 wt %, based on the total weight of the slurry.

For slurries wherein the majority of titanium dioxide particles are of“nano” size, and preferably those in which the average particle size isfrom about 10 nanometers to about 200 nanometers, the amount of titaniumdioxide in the slurry is preferably from about 20 wt % to about 50 wt %,and more preferably from about 25 wt % to about 35 wt %, based on theweight of the slurry.

The titanium dioxide pigment may be substantially pure titanium dioxideor may contain other metal oxides, such as silica, alumina and zirconia.Other metal oxides may become incorporated into the pigment particles,for example, by co-oxidizing or co-precipitating titanium compounds withother metal compounds. If co-oxidized or co-precipitated metals arepresent, they are preferably present as the metal oxide in an amountfrom about 0.1 wt % to about 20 wt %, more preferably from about 0.5 wt% to about 5 wt %, and still more preferably from about 0.5 wt % toabout 1.5 wt %, based on the total titanium dioxide pigment weight.

The titanium dioxide pigment may also bear one or more metal oxidesurface coatings. These coatings may be applied using techniques knownby those skilled in the art. Examples of metal oxide coatings includesilica, alumina, alumina-silica and zirconia, among others. Suchcoatings may optionally be present in an amount of from about 0.1 wt %to about 10 wt %, and preferably from about 0.5 wt % to about 3 wt %,based on the total weight of the titanium dioxide pigment. Commercialexamples of such coated titanium dioxides include R700 (alumina-coated,available from E.I. DuPont de Nemours, Wilmington Del.), RDI-S(alumina-coated, available from Kemira Industrial Chemicals, Helsinki,Finland), R-706 (available from DuPont, Wilmington Del.) and W-6042 (asilica alumina treated nano grade titanium dioxide from TaycoCorporation, Osaka Japan).

The titanium dioxide pigment may also bear one or more organic surfacecoatings, such as, for example, carboxylic acids, silanes, siloxanes andhydrocarbon waxes, and their reaction products with the titanium dioxidesurface. The amount of organic surface coating, when present, generallyranges from about 0.01 wt % to about 6 wt %, preferably from about 0.1wt % to about 3 wt %, more preferably about 0.5 wt % to about 1.5 wt %,and still more preferably about 1 wt %, based on the total weight of thepigment.

Dispersants

Specified combinations of dispersants provide enhanced effects instabilizing titanium dioxide pigment slurries and, furthermore, provideenhanced stability in the ink formulations. The inks of the presentinvention, and the titanium dioxide slurry utilized in making thoseinks, comprise a first dispersant, which is a graft copolymer, a seconddispersant, which is a block copolymer and, optionally, a thirddispersant which is a phosphated polymer. Both the first and seconddispersants preferably contain acid functionality, and can be made watersoluble or dispersible by neutralizing at least a portion of the acidfunctional groups with a base such as ammonia, potassium hydroxide,sodium hydroxide, an amine, such as dimethyl ethyl amine, amino methylpropanol and the like.

The optional third dispersant is a phosphated polymer that is differentfrom the first and second dispersants.

Structured (graft and block) acrylic copolymer dispersant blendsneutralized using dimethyl ethyl amine are preferred.

The inks of the present invention, and titanium dioxide slurry used inthose inks, preferably have an overall dispersant to pigment weightratio (D/P) of from about 0.0025:1 to about 0.25:1, preferably fromabout 0.05:1 to about 0.175:1, and more preferably from about 0.075:1 toabout 0.14:1. The overall dispersant to pigment ratio is the sum totalof D/P contributions from each dispersant present.

The weight ratio of the first and second dispersants is preferably fromabout 10:90 to about 90:10, more preferably from about 25:75 to about75:25, and still more preferably from about 40:60 to about 60:40.

When the optional third dispersant is present, it is preferably presentin an amount of from about 0.0025:1 to about 0.05:1, more preferablyfrom about 0.005:1 to about 0.04:1, and still more preferably from about0.005:1 to 0.02:1, as the weight ratio of third dispersant to pigment.

First Dispersant

Note: All molecular weights referred to herein are determined by GelPermeation Chromatography using polystyrene as a standard.

The first dispersant is a graft copolymer dispersant preferably having aweight average molecular weight of from about 4000 to about 100000, andmore preferably from about 10000 to about 40000. The graft copolymerdispersant can be a block or comb copolymer. Mixtures of more than onegraft copolymer can also be used.

The graft copolymer comprises from about 90% to about 50% by weight of apolymeric backbone and, correspondingly, from about 10% to about 50% byweight of polymeric side chains attached to the backbone (the backboneand side chains together being 100 wt %).

The polymeric backbone is a hydrophobic (relative to the side chains)adsorbing segment. The side chains are individually hydrophilicstabilizing segments. The side chains are attached to the backbone at asingle terminal point.

Backbone

As just indicated, the backbone of the graft copolymer dispersant ishydrophobic relative to the side chains. The backbone comprisespolymerized “non-functional” ethylenically unsaturated hydrophobicmonomers such as alkyl methacrylates and acrylates, and cycloaliphaticmethacrylates and acrylates, such as those listed hereinafter. Thebackbone may still further comprise up to about 20% by weight, andpreferably from about 1% to about 10% by weight, based on the weight ofthe backbone, of polymerized ethylenically unsaturated acid monomers,such as those listed hereinafter, as well as up to about 30% by weight,based on the weight of the backbone, of other polymerized ethylenicallyunsaturated monomers containing functional groups, such as those listedhereinafter.

The backbone of the graft copolymer has an affinity for the surface ofthe pigment used in the slurry and anchors the copolymer to the pigment,thus keeping the pigment dispersed and preventing the graft copolymerfrom returning to the aqueous phase.

Suitable “non-functional” hydrophobic monomers that can be used to formthe hydrophobic adsorbing segment include, but are not limited to, alkyl(meth)acrylates having 1 to 12 (and preferably 1 to 8) carbon atoms inthe alkyl group, and cycloaliphatic (meth)acrylates. Of these, themethacrylates are preferred.

Typical alkyl acrylates and methacrylates that can be used include, forexample, methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate,isopropyl methacrylate, butyl acrylate, butyl methacrylate, pentylacrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate,2-ethyl hexyl acrylate, 2-ethyl hexyl methacrylate, nonyl acrylate,nonyl methacrylate, lauryl acrylate, lauryl methacrylate and the like.

Typical cycloaliphatic acrylates and methacrylates that can be usedinclude, for example, trimethylcyclohexyl acrylate, trimethylcyclohexylmethacrylate, t-butyl cyclohexyl acrylate, isobutylcyclohexylmethacrylate and the like.

Mixtures of “non-functional” ethylenically unsaturated hydrophobicmonomers may be used, for example, mixtures of two or more of any of theabove listed acrylates and methacrylates.

Examples of ethylenically unsaturated acid monomers include methacrylicacid, acrylic acid, itaconic acid, maleic acid and the like; andethylenically unsaturated sulfonic and sulfinic acid and esters thereof,such as styrene sulfonic acid, acrylamido propane sulfonic acid,acrylamido methyl propane sulfonic acid and the like. When used, acrylicand methacrylic acid are preferred.

Examples of functional monomers (other than the ethylenicallyunsaturated acid monomers) include acrylamide, methacrylamide,methacrylonitrile, hydroxy ethyl acrylate, hydroxy ethyl methacrylate,t-butylamino ethyl methacrylate, diethyl amino ethyl acrylate, diethylamino ethyl methacrylate, nitro phenol acrylate, nitro phenolmethacrylate, phthalimido methyl acrylate and phthalimido methacrylate.

Side Chains

The side chains of the graft copolymer are hydrophilic macromonomersthat preferably have a weight average molecular weight of from about1000 to about 30000, and more preferably from about 1500 to about 8000.The side chains preferably comprise from about 2% to about 100% byweight, more preferably from about 20% to about 60% by weight, based onthe weight of the macromonomer, of polymerized ethylenically unsaturated“hydrophilic” monomers, such as ethylenically unsaturated monomerscontaining an acid group or a nonionic hydrophilic group.

When an appropriate amount of the acid functionality is neutralized, theside chains are hydrophilic and keep the pigment uniformly dispersed inthe slurry and in resulting ink.

The side chains can be a mixture of ionic and non-ionic groups ormixtures either in the same side chain or in different side chains.

The macromonomer contains a single terminal ethylenically unsaturatedgroup, which is polymerized into the backbone of the graft copolymer.

It is preferred to use ethylenically unsaturated acid monomers, and morepreferably methacrylic acid, particularly if it is the sole constituentof the macromonomer. Other acid monomers that can be used includeethylenically unsaturated carboxylic acids such as acrylic acid,itaconic acid, maleic acid and the like; and ethylenically unsaturatedsulfonic and sulfinic acid and esters thereof, such as styrene sulfonicacid, acrylamido propane sulfonic acid, acrylamido methyl propanesulfonic acid and the like.

Non-ionic hydrophilic monomers that are useful in the hydrophilicstabilizing segment include monoethylenically unsaturated poly(alkyleneglycol) monomers, such as poly(ethylene glycol) mono (meth)acrylate,poly(ethylene glycol) alkyl ethers having 1 to 4 carbon atoms in thealkyl group (such as poly(ethylene glycol) methyl ether oligomers,supplied under the trade name Bisomer S20W by International SpecialtyChemicals), and the like; and poly(alkoxylated) alkyl (meth)acrylatesand the like. These monomers preferably have a weight average molecularweight of from about 200 to about 4000, and more preferably from about200 to about 2000.

Up to about 80% by weight, based on the weight of the macromonomer, ofother hydrophobic polymerized ethylenically unsaturated monomers can bepresent in the macromonomer, including the “non-functional” alkylacrylates and methacrylates, cycloaliphatic acrylates and methacrylateslisted above.

One preferred macromonomer contains from about 50% to about 80% byweight of polymerized methyl methacrylate, and from about 20% to about50% by weight of polymerized methacrylic acid (100 wt % total), and hasa weight average molecular weight of from about 2000 to about 5000.

The monomers constituting the macromonomer are preferably polymerizedusing a catalytic chain transfer agent that contains a Co⁺² group, i.e.a cobalt chain transfer agent, which ensures that the resultingmacromonomer only has one terminal ethylenically unsaturated group whichwill polymerize with the backbone monomers to form the graft copolymer.Typically, in the first step of the process for preparing themacromonomer, the monomers are blended with an inert organic solvent,which is preferably water miscible or water dispersible, and a cobaltchain transfer agent and heated usually to the reflux temperature of thereaction mixture. In subsequent steps additional monomers, cobalt chaintransfer agent and a conventional azo type polymerization catalyst (suchas 2,2′-azobis(2-methylbutanenitrile),2,2′-azobis(2,4′-dimethylpentanenitrile) and2,2′-azobis(2,4-dimethyl-4-methoxyvaleronitrile)) are added andpolymerization is continued until a macromonomer is formed of thedesired molecular weight. After macromonomer is formed, any solvent maybe stripped off before additional processing to make the firstdispersant graft copolymer.

Preferred cobalt chain transfer agents are described in U.S. Pat. No.4,680,352 and U.S. Pat. No. 4,722,984 (the disclosures of which areincorporated by reference herein for all purposes as if fully setforth). Most preferred are pentacyanocobaltate (II),diaquabis(borondifluorodimethyl-glyoximato) cobaltate (II) anddiaquabis(borondifluorophenylglyoximato) cobaltate (II). Typically thesechain transfer agents are used at concentrations of from about 5 ppm toabout 1000 ppm, based on the weight of the monomers used.

Preparation of First Dispersant

The graft copolymer used in the present invention is preferably preparedby the Special Chain Transfer (SCT) method as described in US5231131(the disclosure of which is incorporated by reference herein as if fullyset forth). By using this method, 100% graft copolymer can beefficiently prepared rather than a mixture of graft copolymer, lowmolecular weight backbone polymer and copolymerized macromonomersegments, as is generally been the case with other processes used formaking graft copolymers. However, it should be recognized that the graftcopolymer dispersant used in this invention is not restricted to anyspecific preparation technology. Graft dispersants of the structure andfunctionality described above made using other known polymerizationtechniques will also provide benefits of this invention and are thuscontemplated to be within the scope of this invention.

To form the graft copolymer, backbone monomers are polymerized in thepresence of solvent, polymerization catalyst and macromonomer prepared,for example, as described above. Any of the aforementioned azo typecatalysts can be used as the polymerization catalyst, as can othersuitable catalysts such as peroxides and hydroperoxides. Typical of suchcatalysts are di-tertiarybutyl peroxide, di-cumyl peroxide, tertiaryamylperoxide, cumenehydroperoxide, di(n-propyl) peroxydicarbonate, peresterssuch as amyl peroxyacetate and the like. Polymerization is continuedusually at the reflux temperature of the reaction mixture until a graftcopolymer is formed of the desired molecular weight.

Typical solvents that can be used to form the macromonomer and/or thegraft copolymer are ketones such as methyl ethyl ketone, isobutylketone, ethyl amyl ketone and acetone; alcohols such as methanol,ethanol and isopropanol; esters such as ethyl acetate; glycols such asethylene glycol and propylene glycol; ethers such as tetrahydrofuran andethylene glycol mono butyl ether; and the like.

After the graft copolymer is formed, the acid functionality thereon canbe at least partially neutralized with, for example, an amine or aninorganic base such as ammonium hydroxide or sodium hydroxide, and thenwater is added to form a dispersion of the graft copolymer. Typicalamines that can be used include amino methyl propanol, amino ethylpropanol, dimethyl ethyl amine, triethylamine and the like. A preferredamine for inkjet applications is dimethyl ethyl amine.

Typically, these first dispersant graft copolymers and the otherdispersants described below are used as from about 20% to about 60%solutions in typical solvents.

Particularly useful graft copolymers include the following:

-   -   a graft copolymer having a backbone of polymerized methyl        acrylate and butyl acrylate, and side chains of a macromonomer        having a weight average molecular weight of from about 2000 to        about 5000, and containing from about 50% to about 80% by        weight, based on the weight of the macromonomer, of polymerized        methyl methacrylate and from about 20% to about 50% by weight,        based on the weight of the macromonomer, of polymerized        methacrylic acid;    -   a graft copolymer having a backbone of polymerized methyl        acrylate, butyl acrylate and acrylamido methyl propane sulfonic        acid, and side chains of the above macromonomer;    -   a graft copolymer having a backbone of polymerized methyl        acrylate, butyl acrylate and acrylic acid, and side chains of        the above macromonomer;    -   a graft copolymer having a backbone of polymerized ethyl        acrylate, and side chains of the above macromonomer;    -   a graft copolymer having a backbone of polymerized ethyl        acrylate, methyl acrylate and acrylic acid, and side chains of        the above macromonomer; and    -   a graft copolymer having a backbone of polymerized ethyl        acrylate and acrylic acid, and side chains of the above        macromonomer.        Second Dispersant

The second dispersant is a block copolymer preferably of type AB, ABA orABC, or mixtures thereof. At least one of the blocks, A, B, or C is anadsorbing segment. At least one of the blocks, A, B, or C is astabilizing segment. By “adsorbing segment” it is meant that the segmentis designed to adsorb onto the surface of a titanium dioxide pigment,for example, by acid-base or other bonding interactions. By “stabilizingsegment” it is meant that the segment is designed to provide a stericstabilization of the pigment particle against flocculation in a slurrycomposition. Generally, the adsorbing segments of the block copolymerare hydrophobic, in comparison to the stabilizing segment, and aredesigned to adhere to the pigment surface, while the stabilizingsegments are generally hydrophilic and are soluble in (aqueous)processing media, for example, media used in finishing crude titaniumdioxide pigment.

The hydrophobic adsorbing segment preferably comprises polymerized“non-functional” ethylenically unsaturated hydrophobic monomers such asare listed hereinafter, and further comprises polymerized ethylenicallyunsaturated monomers having functional groups that enhance the pigmentbinding force. Monomers having functional groups are preferably presentin an amount up to about 40% by weight, based on the total weight of theadsorbing segment. For example, monomers with acid functional groups maybe incorporated in the hydrophobic portion to bind with basic groups onthe titanium dioxide pigment surface. Monomers with amine groups may beincorporated in the hydrophobic portion to bind with acid groups thatmay be present on the titanium dioxide surface. Other functionalmonomers that have known affinity for titanium dioxide, such as monomerswith silane groups, etc., may also be incorporated in the hydrophobicportion.

Suitable “non-functional” hydrophobic monomers that can be used to formthe hydrophobic adsorbing segment include, but are not limited to, alkyl(meth)acrylates having 1 to 12 (and preferably 1 to 8) carbon atoms inthe alkyl group, and cycloaliphatic (meth)acrylates. Of these, themethacrylates are preferred.

Typical alkyl acrylates and methacrylates that can be used include, forexample, methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate,isopropyl methacrylate, butyl acrylate, butyl methacrylate, pentylacrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate,2-ethyl hexyl acrylate, 2-ethyl hexyl methacrylate, nonyl acrylate,nonyl methacrylate, lauryl acrylate, lauryl methacrylate and the like.

Typical cycloaliphatic acrylates and methacrylates that can be usedinclude, for example, trimethylcyclohexyl acrylate, trimethylcyclohexylmethacrylate, t-butyl cyclohexyl acrylate, isobutylcyclohexylmethacrylate and the like.

Mixtures of “non-functional” ethylenically unsaturated hydrophobicmonomers may be used, for example, mixtures of two or more of any of theabove listed acrylates and methacrylates.

Examples of ethylenically unsaturated acid monomers include methacrylicacid, acrylic acid, itaconic acid, maleic acid and the like; andethylenically unsaturated sulfonic and sulfinic acid and esters thereof,such as styrene sulfonic acid, acrylamido propane sulfonic acid,acrylamido methyl propane sulfonic acid and the like. Methacrylic acidis preferred, particularly if it is the sole acid constituent.

Examples of ethylenically unsaturated monomers with amine groups includealkylaminoalkyl methacrylate monomers having 1 to 4 carbon atoms in thealkyl group, such as dimethylaminoethyl methacrylate, diethylaminoethylmethacrylate, dipropylaminoethyl methacrylate, dibutylaminoethylmethacrylate) and the like.

As stated above, the stabilizing segment is preferably soluble in theselected (aqueous) processing medium encountered during crude pigmentfinishing and, therefore, primarily comprises polymerized ethylenicallyunsaturated hydrophilic monomers. Suitable hydrophilic monomers that canbe used to form the stabilizing segment include ethylenicallyunsaturated monomers with an acid group, as well as ethylenicallyunsaturated monomers with a nonionic hydrophilic group, as listed above.

If acid monomers are used, the stabilizing segment is render hydrophilicby neutralizing an appropriate amount of the acid functionality with,for example, an amine (such as dimethyl ethyl amine or 2-amino methylpropanol) and/or an inorganic base (such as ammonium hydroxide or sodiumhydroxide).

In addition to the forgoing monomers, other commonly used hydrophobicmonomers can be copolymerized into the stabilizing portion, providedthey are used at a concentration that will not significantly change thesolubility properties of the stabilizing portion in the selectedprocessing medium. Some useful examples include the alkyl(meth)acrylates and other hydrophobic monomers listed above.

The second dispersant preferably has a number average molecular weightof from about 1000 to about 15000, and more preferably from about 2000to about 5000. The adsorbing segment preferably has a number averagemolecular weight of from about 1000 to about 5000, and more preferablyfrom about 1000 to about 3000. The stabilizing segment preferably has anumber average molecular weight of from about 1000 to about 5000, andmore preferably from about 1000 to about 3000.

The method of preparation of the second dispersant is not critical.Block copolymer dispersants of the structure and functionality describedabove made using known polymerization techniques will provide thebenefits of this invention and are thus contemplated to be within thescope of this invention. The second dispersant may be prepared, forexample, by using the Group Transfer Polymerization (GTP) methodreported in US4656226; or the anionic polymerization method reported byMorton in Anionic Polymerization: Principles and Practice (New York:Academic Press, 1983) (the disclosures of which are incorporated byreference herein for all purposes as if fully set forth).

The GTP method is preferred. An advantage of the GTP process is theability to make polymer dispersants with precise architecture and lowpolydispersity. Typically polydispersity of GTP polymers is betweenabout 1.0 and about 1.25.

Third Dispersant

The optional third dispersant is a phosphated polymer dispersantcomprising a hydrophilic stabilizing segment and a hydrophobic adsorbingsegment. The phosphated polymer can be a graft copolymer, a blockcopolymer or a random copolymer that has phosphate functionality ineither the stabilizing segment, adsorbing segment or both.

The adsorbing segment of the phosphated polymer mainly comprisespolymerized ethylenically unsaturated “non-functional” hydrophobicmonomers, such as alkyl (meth)acrylates, cycloaliphatic (meth)acrylatesand aryl (meth)acrylates, such as are listed hereinafter. The term(meth)acrylate refers to both the acrylate and methacrylate esters.

The adsorbing segment preferably further comprises from about 1% toabout 20% by weight, and more preferably from about 1% to about 10% byweight, based on the total weight of the copolymer, of polymerizedethylenically unsaturated monomers that have attached thereto aphosphate group, or a group that can be converted to a phosphate group,as discussed in further detail below.

Suitable “non-functional” hydrophobic monomers that can be used to formthe hydrophobic adsorbing segment include, but are not limited to, thealkyl (meth)acrylates having 1 to 12 (and preferably 1 to 8) carbonatoms in the alkyl group, cycloaliphatic (meth)acrylates, and mixturesthereof, as described above.

The hydrophilic stabilizing segment of the phosphated dispersantcomprises polymerized ethylenically unsaturated hydrophilic monomers,such as ethylenically unsaturated monomers containing an acid group or anonionic hydrophilic group.

Examples of ethylenically unsaturated acid monomers include methacrylicacid, acrylic acid, itaconic acid, maleic acid and the like;ethylenically unsaturated sulfonic and sulfinic acid and esters thereof,such as styrene sulfonic acid, acrylamido propane sulfonic acid,acrylamido methyl propane sulfonic acid and the like; and ethylenicallyunsaturated phosphoric or phosphonic acid and esters, vinyl phosphonicacid and its esters, and the like.

Non-ionic hydrophilic monomers that are useful in the hydrophilicstabilizing segment include monoethylenically unsaturated poly(alkyleneglycol) monomers, such as poly(ethylene glycol) mono (meth)acrylate,poly(ethylene glycol) alkyl ethers having 1 to 4 carbon atoms in thealkyl group (such as poly(ethylene glycol) methyl ether oligomers,supplied under the trade name Bisomer S20W by International SpecialtyChemicals), and the like; and poly(alkoxylated) alkyl (meth)acrylatesand the like. These monomers preferably have a weight average molecularweight of from about 200 to about 4000, and more preferably from about200 to about 2000. A combination of nonionic and anionic stabilizingsegments can also be favorable.

Phosphate groups can be incorporated into the adsorbing segment or thestabilizing segment by reacting the polymer with phosphoric acid orphosphorus pentoxide. Unreacted or residual phosphoric acid groups arepreferably neutralized with amine or inorganic base when used fordispersing titanium dioxide pigment into water. The remainder of thepolymer may be adjusted to improve dispersibility of the titaniumdioxide pigment and make the copolymer more compatible with othercomponents to form a stabilized pigment slurry.

Alternatively, phosphate groups may be incorporated into the polymer byreaction of a phosphorus containing reactive group with a monomer,macromonomer or polymer such that the resultant optional dispersant is aphosphate-substituted dispersant. An example of this strategy is forminga polymer having reactive hydroxyl groups, for example, by forming acopolymer with hydroxy alkyl methacrylates or acrylates, andsubsequently reacting the hydroxy groups with phosphorus pentoxide.Neutralizing phosphoric acid groups with amine or inorganic base ispreferable for aqueous titanium dioxide slurries.

Suitable monomers with phosphate groups that can also be used tointroduce phosphate groups into the copolymer (adsorbing segment orstabilizing segment) include ethylenically unsaturated phosphatemonomers (such as phosphorylated polyethylene glycol (meth)acrylate,phosphorylated hydroxy ethyl (meth)acrylate, and the like) orethylenically unsaturated monomers containing alcohol groups (such ashydroxy alkyl (meth)acrylate) or epoxy groups (such as glycidyl acrylateand glycidyl (meth)acrylate) which are treated with one or morephosphorylating agents (such as phosphoric acid or phosphorouspentoxide) before or after polymerization to form phosphate groups wherethe epoxy or alcohol groups used to be.

The phosphated copolymer dispersant preferably has a number averagemolecular weight of from about 4000 to about 25000, and more preferablyfrom about 5000 to about 20000. The adsorbing segment typically has anumber average molecular weight of from about 2000 to about 10000, andpreferably from about 4000 to about 7000. The stabilizing segmenttypically has a number average molecular weight of from about 2000 toabout 15000, and preferably from about 4000 to about 7000. The adsorbingsegment typically comprises from about 20% to about 80% by weight of thepolymer, and correspondingly the stabilizing segment typically comprisesfrom about 80% to about 20% by weight of the polymer (the adsorbing andstabilizing segments being 100 wt % total).

The forgoing dispersants may be prepared by a variety of well knownsolution polymerization techniques devised for a particular structure,such as by the GTP (Group Transfer Polymerization) method reported inpreviously incorporated U.S. Pat. No. 4,656,226; by the standard anionicor the free radical polymerization method reported in previouslyincorporated U.S. Pat. No. 4,656,226; or by the SCT method reported inpreviously incorporated U.S. Pat. No. 5,231,131.

The GTP method is traditionally used to form block copolymers. Usingthis method, it is generally recommended to block any acid or hydroxylcontaining monomers to prevent side reactions during polymerization.Following polymerization, the acid and hydroxyl groups are unblocked bya reaction with alcohol or water.

The SCT method is traditionally used to form the macromonomer portion ofa graft copolymer. Macromonomers can also be supplied by other means.

Standard anionic polymerization is oftentimes used to form randomcopolymers and may be used to prepare analogues of resins describedherein.

Titanium Dioxide Slurry

The slurry formed from the titanium dioxide, graft copolymer dispersant,a block copolymer dispersant and optional phosphated polymer, is astable slurry. When settling does occur, the settling is “soft”settling, meaning the titanium dioxide pigment can be readilyre-dispersed and rejuvenated by low shear mixing. The pigment is alsosimilarly stably dispersed when the slurry is formulated into inks, soas not to result in plugging of ink jet nozzles. Low shear mixingincludes, for example, shaking by hand or stirring with an impeller ormixing blades at speeds of less than about 500 rpm wherein no grindingoccurs. In contrast, “hard” settling occurs with many titanium dioxideslurries of the prior art. By hard settling it is meant the settling oftitanium dioxide particles from the slurry cannot be re-dispersed to anacceptable level for ink jet inks.

Liquid Carrier for Preparation of the Titanium Dioxide Slurries

The titanium dioxide slurry used in this invention comprises a liquidcarrier. The carrier is selected from the group consisting of water,glycol ethers and mixtures thereof. The liquid carrier should be capableof providing a stable slurry. Typically the liquid carrier is water, ora mixture of water and a water-miscible co-solvent. Preferably theliquid carrier is an “aqueous” carrier which, in the context of thepresent invention, comprises a predominant amount of water (>50% byweight based on the total weight of the liquid carrier).

Water used in the preparation of the titanium dioxide slurries ispreferably deionized. That is, the water has been treated to removeunwanted ions that may affect the stability and other properties of theslurries. For example, water may be passed through an ion exchangecolumn to remove the unwanted ions. Preferably, the metal ion content ofthe deionized water provides an electrical resistance less than about0.05 micro-ohm-cm electrical resistivity as measured using ASTM method D1125.

Glycol ethers useful in providing titanium dioxide slurries includedipropylene glycol monomethyl ether and propylene glycol normal propylether, for example, those sold by Lyondell Chemical Company under thetrade names Arcosolv® DPM and Arcosolv® PNP, respectively.

Preferably, the liquid carrier for the titanium dioxide slurry isaqueous, and more preferably it comprises water in a predominant amount.

Optional Additives for the Titanium Dioxide Slurry

The titanium dioxide slurry used in the present invention may optionallycomprise one or more optional additives that are compatible with the enduse in inkjet inks.

For example, the titanium dioxide slurry may optionally comprise ahumectant. A humectant may be considered a co-solvent. Typically,although not always, a humectant has a higher boiling point than theprimary solvent, that is, the liquid carrier. A humectant is generallyadded to prevent drying during storage. Humectants may also help retardsettling.

Humectants are especially useful additives to formulations that have apropensity for chalking. Chalking occurs when solvent (that is, liquidcarrier for the slurries of this invention) evaporates, pigment,especially the titanium dioxide pigment, dries on surfaces, and sides ofstorage vessels and may flake off and fall back into the slurry.Chalking can be a serious problem. For example, if dried pigmentagglomerates are introduced into an ink jet formulation, an unacceptablelevel of nozzle outs may occur. Humectants retard solvent evaporationand thereby retard chalking.

Examples of suitable humectants for use in this invention includepolyhydric alcohols such as ethylene glycol, diethylene glycol,propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanedioland 1,2,6-hexanetriol; glycol ethers such as dipropylene glycolmonomethyl ether and propylene glycol normal propyl ether; and othersincluding trimethylolpropane, trimethylolethane, glycerin, polyethyleneglycol and dipropylene glycol. Ethylene glycol is preferred.

The titanium dioxide slurry may also optionally comprise a rheologymodifier. A rheology modifier can be any known commercially availablerheology modifiers, such as Solthix® thickeners available from Avecia.Other useful rheology modifiers include cellulose and synthetichectorite clays. Synthetic hectorite has the formula:[Mg_(w)Li_(x)Si₈O₂₀H_(4-y)F_(z)]²⁻wherein w=3 to 6; x=0 to 3; y=0 to 4; z=12-2w−x, wherein the negativelattice charge is balanced by counterions, and wherein the counterionsare selected from the group consisting of Na⁺, K⁺, NH₄ ⁺, Li⁺, Mg²⁺,Ca²⁺, Ba²⁺, N(CH₃)₄ ⁺, and mixtures thereof. Synthetic hectorite claysare commercially available, for example, from Southern Clay Products,Inc., and include Laponite®; Lucenite SWN®, Laponite S®, Laponite XL®,Laponite RD® and Laponite RDS® brands of synthetic hectorite.Preparation of Titanium Dioxide Slurry

The titanium dioxide slurry used in this invention can be prepared bymixing the components in a mixing vessel. Components can be addedsequentially or simultaneously in any order. The following provides atypical process to prepare the slurry, but should not be consideredlimiting. Typically, a two-step process is used involving a first mixingstep followed by a second grinding step. The first step comprises mixingall of the ingredients, that is, titanium dioxide pigment, dispersants,liquid carrier and any optional additives to provide a blended“pre-mix”. Mixing generally occurs in a stirred vessel. High-speeddispersers are particularly suitable for the mixing step. Preferably,the dispersants are combined before introducing into the mixture ofother ingredients. The combined dispersants are typically addedincrementally.

The second step comprises grinding of the pre-mix to produce a titaniumdioxide slurry. Preferably grinding occurs by media milling althoughother techniques can be used. Following a grinding step, the slurry isfiltered. Filtration can be performed using any means known in the art,and is typically accomplished by use of standard, commercially availablefilters between 1 and 10 microns in size.

Preparation of Inks

The inks of this invention are preferably made from the titanium dioxideslurries described above, by conventional process known to the art. Thatis, the titanium oxide slurry is processed by routine operations tobecome an ink which can be successfully jetted in an inkjet system.

Typically, in preparing an ink, all ingredients except the pigmentslurry are first mixed together. After the other ingredients are mixed,the slurry is added. Common ingredients in ink formulations useful withthe titanium dioxide slurries include one or more humectants, aco-solvent, one or more surfactants and biocide. A typical ink using thetitanium dioxide slurry will have the following formulation: IngredientWeight % TiO₂ Slurry* 0.7-50% Humectant(s)   5-20% Co-Solvent   5-30%Surfactant(s) 0.5-1.0% Biocide 0.15% Water 0 to 70% Total  100%*Solids content ˜70%; includes TiO₂ and dispersants

The titanium dioxide slurry used in this invention utilizes a specificmixture of dispersants in specific amounts to stabilize and keep thepigments deflocculated over long periods of time both in slurry form andwhen the slurry is subsequently used in an ink formulation. As a result,the ink formulation is stable and non-flocculated or agglomerated andhas other advantageous properties when applied to surfaces as an ink.The neutralization of the dispersants can depend on the final vehicleuse in the ink, the printed substrate etc.

Alternatively, the ink may be prepared without the intervening step ofpreparing a pigment slurry. That is, the TiO₂ pigment and otheringredients of the ink can be combined in any order and this mixture issubject to dispersing mixing. The intensity of the mixing can range frommilling using a ball mill with or more intense dispersive mixing such asHSD, roll milling or media milling can be used to obtain the final inkformulation. There are no constraints on the milling media.

Ink Vehicle

The ink vehicle is an aqueous vehicle comprising water and, optionally,one or more water-miscible cosolvents. Representative examples ofwater-miscible co-solvents are disclosed in U.S. Pat. No. 5,085,698 (thedisclosure of which is incorporated by reference herein for all purposesas if fully set forth). The proportion of ingredients in the aqueousvehicle should be such as to result in an aqueous inkjet ink having awater content of greater than about 10 wt %, and preferably greater thanabout 25 wt %, based on the total ink weight.

If a mixture of water and a water-soluble solvent is used, the aqueousvehicle typically will contain from about 25% to about 95% water withthe balance (i.e., about 75% to about 5%) being the water-solublesolvent.

The amount of aqueous vehicle in the ink (non-solids) is typically inthe range of about 70% to about 99.8%, and preferably about 80% to about99.8%, based on total weight of the ink.

Other Ingredients

The inks may optionally contain one or more other ingredients such as,for example, surfactants, binders, bactericides, fungicides, algicides,sequestering agents, buffering agents, corrosion inhibitors, lightstabilizers, anti-curl agents, thickeners, and/or other additives andadjuvants well-known in the relevant art.

Additional dispersants can be added to the ink system to obtain stableink dispersions. Examples of other dispersants that can beadvantageously used are Disperbyk® 2000 and 2001 from Byk Chemie.

These other ingredients may be formulated into the inks and used inaccordance with this invention, to the extent that such otheringredients do not interfere with the stability and jettability of theink, which may be readily determined by routine experimentation. Theinks may be adapted by these additives to the requirements of aparticular inkjet printer to provide an appropriate balance ofproperties such as, for instance, viscosity and surface tension, and/ormay be used to improve various properties or functions of the inks asneeded.

The amount of each ingredient must be properly determined, but istypically in the range of from about 0 to about 15% by weight and moretypically from about 0.1% to about 10% by weight, based on the totalweight of the ink.

Surfactants may be used and useful examples include ethoxylatedacetylene diols (e.g. Surfynols® series from Air Products), ethoxylatedprimary (e.g. Neodol® series from Shell) and secondary (e.g. Tergitol®series from Union Carbide) alcohols, sulfosuccinates (e.g. Aerosol®series from Cytec), organosilicones (e.g. Silwet® series from Witco) andfluoro surfactants (e.g. Zonyl® series from DuPont). Surfactants, ifused, are typically in the amount of from about 0.01 to about 5% andpreferably from about 0.2 to about 2%, based on the total weight of theink.

Binders may be also used and can be soluble or dispersed polymer(s),added to the ink to improve the adhesion of a pigment. Examples ofpolymers that can be used include polyesters, polystyrene/acrylates,sulfonated polyesters, polyurethanes, polyimides and the like. Whenpresent, soluble polymer is advantageously used at levels of at leastabout 0.3%, and preferably at least about 0.6%, based on the totalweight of the ink. Upper limits are dictated by ink viscosity or otherphysical limitations.

When the substrates used with the invention are porous, such as paperand textiles, binders can be added to reduce the penetration of the inkinto the substrates. In other words with these additives, the ink willremain more on the surface of the porous substrate and the opacityhiding power and other printing parameters for the ink will be improved.

Ink Properties

Jet velocity, drop size and stability are greatly affected by thesurface tension and the viscosity of the ink. Inkjet inks typically havea surface tension in the range of about 20 dyne/cm to about 60 dyne/cmat 25° C. Viscosity can be as high as 30 cps at 25° C. (30 cps or less),but is typically somewhat lower. The inks have physical propertiescompatible with a wide range of ejecting conditions, i.e., drivingfrequency of the piezo element, or ejection conditions for a thermalhead, for either a drop-on-demand device or a continuous device, and theshape and size of the nozzle. The inks of this invention should haveexcellent storage stability for long periods so as not clog to asignificant extent in an ink jet apparatus. Further, it should not alterthe materials of construction of the ink jet printing device it comes incontact with, and be essentially odorless and non-toxic.

Although not restricted to any particular viscosity range or printhead,the inventive inks are suited to lower viscosity applications such asthose required by higher resolution (higher dpi) printheads that jetsmall droplet volumes, e.g. less than about 20 pL. Thus the viscosity(at 25° C.) of the inventive inks can be less than about 7 cps, ispreferably less than about 5 cps, and most advantageously is less thanabout 3.5 cps.

The inks of this invention are sufficiently stable to be effectiveinkjet inks. When tested by heating the inks for one week at 70° C., thephysical parameters of particle size and viscosity should be in normalbounds. The inks should also be printable from the desired printingsystem for multiple days, without any observable decrease inperformance.

Ink Sets

Ink sets contain the ink described above, and one or more other inks.The non-white inks of the ink set contain other colorants, andpreferably other pigment colorants. By definition, pigments do not form(to a significant degree) a solution in the vehicle and must bedispersed. Other pigments for inkjet applications are generally wellknown. A representative selection of such pigments are found, forexample, in U.S. Pat. No. 5,026,427, U.S. Pat. No. 5,086,698, U.S. Pat.No. 5,141,556, U.S. Pat. No. 5,169,436 and U.S. Pat. No. 6,160,370, thedisclosures of which are incorporated by reference herein for allpurposes as if fully set forth. The exact choice of pigment will dependupon color reproduction and print quality requirements of theapplication.

The levels of pigment employed in the other inks of the ink set arethose levels that are typically needed to impart the desired OD to theprinted image. Typically, such pigment levels are in the range of fromabout 0.01 to about 10% by weight, based on the total weight of the ink.

The other inks of the ink set can be aqueous or non-aqueous. The choicebetween the two systems is dictated by the requirements for matching theink system to the printed substrate. For paper and textile substrates,aqueous systems are typically preferred. However, for plastic substratesnon-aqueous vehicles may be preferred.

Other aqueous inks of the ink set may contain dyes, pigments orcombinations thereof as the colorant. Such other aqueous inks are basedon aqueous vehicles and other components and additives as describedabove or as otherwise are known to those of ordinary skill in the artand may, in a general sense, be considered known to those of ordinaryskill in the art. Selection of other aqueous inks for the ink set canreadily be made based upon the desired end use and compatibility withthe inks of the present invention.

Non-aqueous inks generally comprise a colorant (preferably a pigment) ina “non-aqueous vehicle”, which refers to a vehicle that is substantiallycomprised of a nonaqueous solvent or mixtures of such solvents, whichsolvents can be polar and/or nonpolar. Examples of polar solventsinclude alcohols, esters, ketones and ethers. Specific examples includemono- and di-alkyl ethers of glycols and polyglycols, such as monomethylethers of mono-, di- and tri-propylene glycols, and the mono-n-butylethers of ethylene, diethylene and triethylene glycols and glycerol andsubstituted glycerols. Examples of nonpolar solvents include aliphaticand aromatic hydrocarbons having at least six carton atoms, and mixturesthereof including refinery distillation products and by-products. Thesolvents may also be comprised in part, or entirely, or polymerizablesolvents such as solvents which cure upon application of UV light (UVcurable).

Glycol ethers include ethylene glycol monobutyl ether, diethylene glycolmono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethyleneglycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether,ethylene glycol mono-t-butyl ether, diethylene glycol mono-n-butylether, triethylene glycol mono-n-butyl ether, diethylene glycolmono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycolmono-t-butyl ether, propylene glycol mono-n-propyl ether, propyleneglycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether,dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propylether, and dipropylene glycol mono-isopropyl ether. Also useful areesters, especially acetate esters, of the preceding glycol ethers.

Even when no water is deliberately added to the non-aqueous vehicle,some adventitious water may be carried into the formulation, butgenerally this will be no more than about 2% to about 4% by weight,based on the total vehicle weight. By definition, the non-aqueous ink ofthis invention will have no more than about 10%, and preferably no morethan about 5%, by weight of water based on the total weight of thenon-aqueous vehicle.

Non-aqueous inks for inkjet applications also are in general well-knownto those of ordinary skill in the art. Selection of non-aqueous inks forthe ink set can readily be made based upon the desired end use andcompatibility with the aqueous inks of the present invention.

Preferred non-aqueous inks for use in an ink set in combination with theink of the present invention are disclosed in U.S. application Ser. No.10/644,323 (filed Aug. 20, 2003), the disclosure of which isincorporated by reference herein for all purposes as if fully set forth.

The ink sets containing a white ink provide significant new breadth toprinting capabilities. In one preferred embodiment, the ink setpreferably comprises at least four differently colored inks—in additionto a white ink, the ink sets also contains a cyan, magenta and yellowink. In addition to white and CMY, it may also be preferred that the inksets further comprise a black ink.

In another preferred embodiment, the ink sets comprise a white ink and ablack ink.

Methods of Printing

The inks and ink sets of the present invention can be utilized byprinting with any inkjet printer.

The method of printing in accordance with the invention comprises thesteps of:

-   (a) providing an ink jet printer that is responsive to digital data    signals;-   (b) loading the printer with a substrate to be printed;-   (c) loading the printer with the above-mentioned inks and/or ink    sets;-   (d) printing onto the substrate using the inkjet ink set in response    to the digital data signals.

When printing on a transparent substrate, like polyvinyl butyral, it issometimes desirable for the image to only appear on one side or bevisible from both sides. If the image is to be visible only on one side,the white ink could be printed first and printed in the shape of theimage and with adjustable opaqueness such that the image would onlyappear from one side. The opaqueness can be adjusted by a variety ofmeans including changing the titanium dioxide concentration in the ink,printing multiple times, etc.

If the image is to be seen from both sides then the white ink can be useto provide more flexibility to the image through the use of white. Itsinclusion in parts of the image can improve the whiteness of imageareas, and the clarity of the image. Nanograde titanium dioxide with itsbetter transparency would be preferred in this application.

When printing on textiles, the white ink of this invention can provideother benefits. Often when textiles are printed the ink will featherinto the textile giving an indistinct boundary. The white ink could beuse to print a small, imperceptible boundary to a design and making itappear to have a distinct boundary.

The titanium dioxide white ink, since it is stable, can be added toanother ink to provide a pigmented ink with both a pigment and atitanium dioxide pigment. While a white ink/pigmented ink would belighter than the pigmented ink, it would retain the covering power andother beneficial properties of a combined ink because of the inclusionof the white ink.

Printed Substrates

The inks and ink sets can be used to print many substrates includingpaper, especially colored papers, packaging materials, textiles andpolymer substrates. The instant invention is particularly advantageousfor printing on polymeric (non-porous) substrates such as polyvinylbutyral interlayer (including 15 and 30 mil thickness); spun bondedpolyolefin (e.g. Tyvek® and Tyvek® JetSmart, DuPont); polyvinyl chloride(e.g., Tedlar®, DuPont); polyethylene terephthalate polyester; polyvinylfluoride polymer, acrylics (e.g., Surlyn®, DuPont) and the like.

A particularly preferred use for the ink sets of the present inventionis the decorative printing of polyvinyl butyral interlayers used insafety or architectural glass applications, such as disclosed incommonly owned WO2004018197 entitled “Decorative Laminated SafetyGlass”, the disclosure of which is incorporated by reference herein forall purposes as if fully set forth.

EXAMPLES

Various abbreviations used in these Examples are listed below. DPMdipropylene glycol methyl ether DPMA gipropylene glycol methyl etheracetate TPnP tripropylene glycol propyl ether DPnP dipropylene glycolpropyl ether TPM tripropylene glycol methyl ether DMEA Dimethylethylamine PNP propylene glycol n-propyl ether cps centipoise nBAn-butyl acrylate MA methyl acrylate AA acrylic acid MAA methacrylic acidMMA methyl methacrylate GMA glycidyl methacrylateMethods

Titanium dioxide slurries were prepared from titanium dioxide pigments,dispersants, water and optional additives using a Dispermat® High SpeedDisperser (HSD), available from VMA-Getzmann GMBH, to premix ingredientsfollowed by media milling using an Eiger minimill, available from EigerMachinery, Inc. Premixing of all slurry ingredients was performed usinga Model AE5—CEX Dispermat operated typically at 2000 rpm with anattached 60 mm Cowels blade. Slurry premix was loaded into a 1-literstainless steel vessel for media milling.

Slurry viscosity at a specific pigment loading was used to assessdispersant effectiveness. The most effective dispersant or combinationof dispersants produced slurries with the lowest viscosity. Slurryviscosity was measured using a Brookfield viscometer and model RVTDV-IIwith measurements taken at 10 and 100 spindle rpm. Viscosity units areCentipoise (cps).

Titanium Dioxide Pigments

Commercially available titanium dioxide pigments were used. Twoalumina-coated titanium dioxide pigments were used, R700 (available fromE.I. DuPont de Nemours, Wilmington Del.) and RDI-S (available fromKemira Industrial Chemicals, Helsinki, Finland).

Ink Formulation and Evaluation

The inks were prepared by methods known to one skilled in the art,unless otherwise noted. Dispersions of the pigments (pigment slurries)were first prepared and, in a separate step, the ink components werecombined and mixed together by ball milling, media milling, or othermixing means. In general 0.8 to 1.0 micron zirconia was used for themilling. After the ink was milled, it was filtered through a 1-micronfilter paper to remove the media. If the ink did not filter well, it wasnot tested in a printer.

Printing Tests

Any printer can be used to test these white inks. Unless otherwisenoted, the examples described below were done using an Epson 3000 inkjet printer and prints were made on various substrates. The white inkwas used in place of the black ink and images were produced usingPhotoShop Software.

Dispersant Preparation

In general, dispersants were prepared in a non-neutralized form andneutralization was done at the end of preparation, in a separatesubsequent step, or after the mixture of dispersants was prepared. Thedispersants were used as 25% to 50% by weight solution in common organicsolvents. The amount of dispersant listed in the examples below wastotal weight of the added solution, not the active ingredients. Whereratios of dispersants to pigments are described, the ratio is given asactive ingredients.

First Dispersant

The first dispersant, Dispersant 1, was a graft polymer with a comb-likestructure, and its molecular configuration was:

-   -   nBA/MA/AA (45.5/45.5/9) 1 g-MMA/MAA (71.25/28.75)        The above representation illustrates the polymer backbone made        up 69% of the polymer (nBA/MA/AA) wherein nBA is n-butyl        acrylate, MA is methyl acrylate and AA is acrylic acid. The        notation (45.5/45.5/9) indicates the relative percents of each        monomer, that is, 45.5% n-butyl acrylate, 45.5% methyl acrylate,        and 9% acrylic acid. The arms, which were the macromonomer, were        31% of the total polymer (g-MMA/MAA), wherein g-M MA is methyl        methacrylate and MAA is methacrylic acid, present in amounts of        71.25% and 28.75%, respectively. In this representation of the        dispersants, a double slash indicates a separation between        blocks, and a single slash indicates a random copolymer within a        block.

The acid groups on the polymer were neutralized with dimethyl ethylamine(DMEA).

Second Dispersant

The second dispersant was one of three different block copolymersprepared using the GTP method disclosed in previously incorporated U.S.Pat. No. 4,656,226. One of these dispersants, Dispersant 2A, had amolecular configuration of

-   -   BMA/MAA//MAA 13/5//10        wherein BMA is butyl methacrylate and MM is methacrylic acid.

In this representation, which is different from the representation forthe graft copolymer, the notation 13/5//10 indicates a block copolymerwith the respective number of monomers. That is, one block is a randomcopolymer having 13 monomer units of BMA and 5 monomer units of MAA. Thesecond block has10 monomer units of MAA.

The second block copolymer dispersant, Dispersant 2B, had a molecularconfiguration of:

-   -   BMA//MAA 13//10        wherein BMA and MAA are as defined above. The notation 13//10        indicates 13 monomer units of BMA and 10 monomer units of MAA in        the block copolymer.

The third block copolymer dispersant, Dispersant 2C, had a molecularconfiguration of:

-   -   BMA//MMA/MAA 10//5/10        wherein BMA, MMA and MAA are as defined above. The notation        10//5/10 indicates one block is a BMA polymer having 10 monomer        units. The second block is a random copolymer having 5 monomer        units of MMA and 10 monomer units of MAA.        Third Dispersant

The third dispersant was a phosphated acrylic comb copolymer containingphosphate functionality in the pigment adsorbing backbone segment andprepared using a standard free radical polymerization approach. Theresulting phosphated copolymer had the following composition:

-   -   nBA/MA/GMA-Phosphated (45.5/45.5/9)//Bisomer 20W        The weight ratio of the phosphated portion to the Bisomer was        60:40.

The phosphate polymer was prepared using the macromonomer, Bisomer 20W,available from International Specialty Chemicals, as the stabilizingarms of the polymer. This material is a macromonomer of poly(ethyleneglycol monomethacrylate). It is nonionic with a molecular weight, Mw of2000 and provides the water-soluble functionality to the polymer. TheBisomer 20W macromonomer, along with other ingredients, were reacted ina vessel to form the macro branched graft copolymer.

The polymer was formed by charging a reactor equipped with a stirrer,thermocouple, condenser and nitrogen blanket, and heating the contentsto reflux. To the reactor, the backbone monomers of n-butyl acrylate(nBA), glycidyl methacrylate (GMA), methyl acrylate (MA) and the Bisomer20W macromonomer were added with isopropanol as the solvent. Thepolymerization reaction was initiated by feeding the initiator2,2′-azobis(2,4-dimethylvaleronitrile) (Vazo® 52 from DuPont Co.) whichwas dissolved in a solution of methyl ethyl ketone and isopropanol. Thephosphating was accomplished by an esterification of the epoxy groups onglycidyl methacrylate with phosphoric acid, H₃PO₄. The resultingphosphate acrylic graft copolymer reached 99% conversion. Its solids was45% in a solution of water/isopropanol. The molecular weight of thepolymer was obtained using GPC. The polymer was methylated prior toinjection into the column. The GPC indicated a number average molecularweight of 4577 and a polydispersity of 2.64.

PIGMENT SLURRY EXAMPLES (SLURRY EX) 1-4

Slurries based on dispersant blends were prepared using using a ModelAE5-CEX Dispersmat operated at 2000 rpm with an attached 60 mm Cowelsblade. Dispersant 1 and Dispersant 2A were mixed together in either75:25 or 50:50 blends (Dispersant 1:Dispersant 2A). Addition of thedispersant blend was slow and incremental to the titanium dioxideslurry. Composition information (in grams) and results are presented inTables 1 and 2. TABLE 1 Slurry Examples 1-4, Compositions Slurry SlurryEx 1 Ex 2 Slurry Ex 3 Slurry Ex 4 Composition Amount, g Amount, gAmount, g Amount, g Deionized water 188.45 188.45 188.45 188.45 DMEA 0.50.5 0.5 0.5 Dispersant Blend 20 0 20 0 50:50 Dispersant Blend 0 20 0 2075:25 Dehydran ® 1620 1 1 1 1 R700 Pigment 720 720 0 0 RDIS Pigment 0 0720 720 Let down 70.05 70.05 70.05 70.05 deionized water

TABLE 2 Slurry Examples 1-4, Viscosities Slurry Analysis Ex 1 Slurry Ex2 Slurry Ex 3 Slurry Ex 4 Solids, % 72.43 72.1 Brookfield Viscosity 6468 66 66 20 rpm Brookfield Viscosity 91.6 95.2 100 101 100 rpm

As can be seen from Table 2, by blending two dispersants together, adesirable viscosity is achieved.

Stability testing was performed by exposing each slurry to 70° C. forone week. The slurries containing dispersant blends were generallystable and had less hard settling upon storage, but were susceptible tosome chalking.

SLURRY EX 5

A titanium dioxide slurry with reduced chalking was prepared by mixing138.45 g deionized water with 720 g of R700 TiO₂ pigment, 50 g ofethylene glycol as a humectant, 18.5 g of a 50:50 blend of Dispersant 1and Dispersant 2B, 1 g DMEA and 2 g Dehydran® 1620. The slurry was letdown with 70.05 g deionized water. Brookfield viscosity is shown inTable 3. TABLE 3 Slurry Example 5, Properties Analysis Before let downAfter let down Brookfield viscosity 20 rpm 795 104 Brookfield viscosity100 rpm 448 130 Solids, % 78.35 72.6

This sample showed improved stability and less chalking after heating at70° C. for 1 week than did the slurries of Slurry Exs 1-4.

SLURRY EX 6

Titanium dioxide slurry premix was prepared by charging 138.45 g water,1 g of 50% DMEA in water, 20 g of a 50:50 blend of Dispersant 1 andDispersant 2B (37% solids), 50 g ethylene glycol, 2 g Dehydran® 1620 and720 g of R700 pigment into a 1-liter stainless steel vessel, andprocessing for 10 minutes at 2000 rpm using a Dispermat High SpeedDisperser configured with a 60 mm Cowels blade. The premix was let downwith 68.55 g water, stirring at 250 rpm for 5 minutes.

The premix was then processed on an Eiger Mini Mill, model MK II M250VSE EXP for 15 minutes at 3250 rpm disc speed with a 480 g media chargeof 0.8-1.0 mm zirconia. Grinding was continued for 30 minutes withsampling at 10, 15, 20 and 30 minutes to determine particle size. Thefinal product was about 72% solids. Results are provided in Table 4before and after let down. TABLE 4 Slurry Example 6 Particle Size vs.Milling Time Particle size, Median Particle Size c <204 nm 50% 95% 10minutes 30.82 240.2 395.9 15 minutes 18.68 235.9 293.8 20 minutes 26.42246.7 380.9

This slurry product was stable over time and used in preparing whiteinks.

INK EXAMPLE (INK EX) 1, 2 AND 3

The titanium dioxide slurry prepared in Slurry Ex 6 was used to prepareink formulations in which the titanium dioxide solids loading was 5%(Ink Ex 1), 6% (Ink Ex 2) and 7% (Ink Ex 3). Slurry Ex 6 was firstdiluted with deionized water to obtain a slurry with a 15 wt % TiO₂content (based on the total weight of the diluted slurry). An ink premixwas prepared by adding together and mixing ink formulation ingredientslisted below in Table 5. All of the ingredients were premixed prior toaddition of the 15 wt % titanium dioxide slurry. The 5% and 6% inks wereprepared by the same process by simply adjusting the amount of dilutedslurry added, to achieve the desired final concentration of titaniumdioxide in the final ink. TABLE 5 Ink Example 3, Compositions Added InkIngredient Weight % in Ink Titanium dioxide slurry 47 Ethylene Glycol13.5 Glycerol 13.5 Proxel ® (biocide) 0.16 Deionized water BalanceSilwet L-77 ® (surfactant) 0.15 Surfynol ® 104E (defoamer) 0.15

Proxel® GXL is a biocide available from Avecia, Inc. Silwet L-77® is asurfactant available from GE Silicones. Surfynol® 104E is a defoameravailable from Air Products.

Premix (ink without the titanium dioxide slurry) was mixed for 1 hour.With continuous mixing, the titanium dioxide slurry of Slurry Ex 6 wasadded to the premix by pumping the premix into the titanium dioxideslurry with recirculation through a feed tube. The ink was stirred for 4hours.

Viscosity was measured, then the ink was filtered through a 1 micronfiltration apparatus, removing large agglomerates, aggregates andparticulates. Table 12 provides analysis of the inks. Particle size wasmeasured using a Microtrac® Ultrafine Particle Analyzer (UPA) availablefrom Leeds and Northrup. TABLE 6 Ink Examples 1-3, Properties BrookfieldParticle Ink TiO₂ Viscosity size Microtrac Particle Size Ex loading, %30 rpm 100 rpm <204 nm) 50%, nm 95%, nm 1 5 2.44 2.47 1.07 258.5 308.0 26 2.46 2.47 0 295.0 345.9 3 7 2.46 2.44 0 385.4 547.1

The inks were tested for stability by placing the samples in an oven for7 days at 70° C. Viscosity and particle size were compared before andafter to assess stability of ink over time. Results are provided inTable 7. TABLE 7 Ink Ex 1-3, Brookfield Viscosity and Properties after 7days in the oven at 70° C. Pigment Before After Ink Ex Loading, % 30rpms 60 rpms 30 rpms 60 rpms 1 5 1.42 1.20 1.30 1.30 2 6 1.22 1.21 1.201.17 3 7 1.80 1.93 1.82 1.86 Before After Ink Ex <204 nm 50% 95% <204 nm50% 95% 1 19.37 290.0 498.4 0 261.8 301.2 2 0 306.2 378.4 0 308.5 360.93 7.33 266.2 362.1 1.32 251.9 296.1

Results for Ink Examples 1-3 listed in Table 7 show stability in the inkformulations, in that separation and particle settling were notobserved.

Ink Ex 1, 2 and 3 were tested using a Piezo drop on demand (DOD)printhead consisting of 255 nozzles each with an average diameter of 50microns. The volume of each droplet of ink was approximately 35picoliters. The velocity through each nozzle was about 5 m/s. Ink wasjetted out onto a clear overhead transparency film and black paper. Thehiding power and opacity on the transparency film was judged asexcellent and the adhesion to the transparency was also considered good.No nozzle outs resulted for Ink Ex 2 and 3. For Ink Ex 1 one nozzle outwas observed.

INK EXAMPLE 4

Ink Example 4 was prepared by diluting Slurry Ex 6 with water to obtaina titanium dioxide slurry with 15% solids (79.2 grams of water added to20.8 grams of Slurry Ex 6 to make a 6% solids ink). This diluted slurrywas converted into an ink with the following formulation. TABLE 8 InkExample 4 Formulation Slurry 6 diluted to 15% solids 40 DPM 36.92 DPnP24.61 PYK 0.5 pigment solids, (%) 6.00 Viscosity 7.56 Surface Tension26.37

Ink Ex 4 was printed onto a polyvinyl butyral interlayer. The interlayerwas used to produce a decorative laminate as described in previouslyincorporated WO2004018197. The polyvinyl butyral interlayer was printedin a rectangle configuration in multiple passes to test for the %transmission, % haze and % clarity. Each pass was set for printing 100%coverage. After printing, the vinyl butyral interlayer was used to makea decorative laminate. A BKY Gardner Hazegard Plus Instrument was usedto measure the % T, % H, and % C. Haze (wide angle scattering) isdefined as the percentage of transmitted light that in passing through asample deviates from the incident beam by more than 2.50. Clarity(narrow angle scattering) is measured as scattering at less than 2.5°.TABLE 9 Ink Ex 4, White Ink Printed Decorative Laminates Number ofprinting passes Glass type % Transmission % Haze % Clarity 1 Clear 65.851.9 90.3 2 Clear 55.4 72.6 80.6 3 Clear 49.8 81.4 74.7 4 Clear 46.185.6 70.3 5 Clear 45.6 87.5 68.5 1 Starphire 66.2 49.3 90.7 2 Starphire54.6 71.4 81.4 3 Starphire 48.5 80.3 75 4 Starphire 44.9 84.1 71 5Starphire 42.1 86.7 69.4

The ‘Clear’ Glass is normal glass made by the float process, and it hada slightly green tint. The Starphire glass was the PPG “ultra-white”glass.

Test for Whiteness and Yellowness of White Ink Printed Substrates

The polyvinyl butyral decorative laminate used with Ink Ex 4 was testedfor whiteness as measured by ASTM E 313, and yellowness as measured byASTM D1925. The Whiteness Index was 45.12, and the Yellowness Indexwas—2.2.

1. An aqueous inkjet ink comprising an aqueous vehicle having dispersedtherein: (a) a titanium dioxide pigment; (b) a combination ofdispersants comprising: (1) a graft copolymer having a weight averagemolecular weight of from about 4000 to about 100000, comprising fromabout 90% to about 50% by weight of a polymeric backbone, and from about10% to about 50% by weight of macromonomer side chains attached to thebackbone, the polymeric backbone and macromonomer side chains comprising100 wt % of the graft copolymer, wherein: (i) the polymeric backbone ishydrophobic in comparison to the macromonomer side chains and comprisesone or more polymerized ethylenically unsaturated hydrophobic monomersand, optionally, up to about 20% by weight, based on the weight of thegraft copolymer, of polymerized ethylenically unsaturated acid monomers;and (ii) each of the macromonomer side chains individually is ahydrophilic polymer containing acids groups attached to the polymericbackbone at a single terminal point, and (A) has a weight averagemolecular weight of from about 1000 to about 30000, and (B) comprisesfrom about 2% to about 100% by weight, based on the weight of themacromonomer side chain, of a polymerized ethylenically unsaturated acidmonomer, and (C) wherein the acid groups are at least partiallyneutralized, preferably with an inorganic base and/or an amine; (2) ablock copolymer of type AB, ABA or ABC wherein at least one of theblocks in the block copolymer is an adsorbing segment, and wherein atleast one of the blocks in the block copolymer is a stabilizing segment.2. The aqueous inkjet ink of claim 1, further comprising a phosphatedacrylic copolymer, different from the graft copolymer (b)(1) or blockcopolymer (b)(2), comprising a hydrophilic stabilizing segment and ahydrophobic adsorbing segment.
 3. The aqueous inkjet ink of claim 1,which is white.
 4. An aqueous inkjet ink comprising a vehicle to whichhas been added an aqueous titanium dioxide slurry comprising: (a) atitanium dioxide pigment; and (b) a combination of dispersantscomprising: (1) a graft copolymer having a weight average molecularweight of from about 4000 to about 100000, comprising from about 90% toabout 50% by weight of a polymeric backbone, and from about 10% to about50% by weight of macromonomer side chains attached to the backbone, thepolymeric backbone and macromonomer side chains comprising 100 wt % ofthe graft copolymer, wherein: (i) the polymeric backbone is hydrophobicin comparison to the macromonomer side chains and comprises polymerizedethylenically unsaturated hydrophobic monomers and, optionally, up toabout 20% by weight, based on the weight of the graft copolymer, ofpolymerized ethylenically unsaturated acid monomers; and (ii) each ofthe macromonomer side chains individually is a hydrophilic polymercontaining acids groups attached to the polymeric backbone at a singleterminal point, and (A) has a weight average molecular weight of fromabout 1000 to about 30000, and (B) comprises from about 2% to about 100%by weight, based on the weight of the macromonomer side chain, of apolymerized ethylenically unsaturated acid monomer, and (C) wherein theacid groups are at least partially neutralized with an inorganic base oran amine; (2) a block copolymer of type AB, ABA or ABC wherein at leastone of the blocks in the block copolymer is an adsorbing segment, andwherein at least one of the blocks in the block copolymer is astabilizing segment; and (c) a liquid carrier.
 5. The aqueous inkjet inkof claim 4, wherein the titanium dioxide slurry further comprises aphosphated acrylic copolymer, different from the graft copolymer (b)(1)or block copolymer (b)(2), comprising a hydrophilic stabilizing segmentand a hydrophobic adsorbing segment.
 6. The aqueous inkjet ink of claim4, which is white.
 7. The aqueous inkjet ink of claim 4, wherein theliquid carrier is an aqueous carrier.
 8. An inkjet ink set comprising aplurality of colored, pigmented inks, at least one of which is a firstaqueous inkjet ink comprising an aqueous vehicle having dispersedtherein: (a) a titanium dioxide pigment; (b) a combination ofdispersants comprising: (1) a graft copolymer having a weight averagemolecular weight of from about 4000 to about 100000, comprising fromabout 90% to about 50% by weight of a polymeric backbone, and from about10% to about 50% by weight of macromonomer side chains attached to thebackbone, the polymeric backbone and macromonomer side chains comprising100 wt % of the graft copolymer, wherein: (i) the polymeric backbone ishydrophobic in comparison to the macromonomer side chains and comprisesone or more polymerized ethylenically unsaturated hydrophobic monomersand, optionally, up to about 20% by weight, based on the weight of thegraft copolymer, of polymerized ethylenically unsaturated acid monomers;and (ii) each of the macromonomer side chains individually is ahydrophilic polymer containing acids groups attached to the polymericbackbone at a single terminal point, and (A) has a weight averagemolecular weight of from about 1000 to about 30000, and (B) comprisesfrom about 2% to about 100% by weight, based on the weight of themacromonomer side chain, of a polymerized ethylenically unsaturated acidmonomer, and (C) wherein the acid groups are at least partiallyneutralized, preferably with an inorganic base and/or an amine; (2) ablock copolymer of type AB, ABA or ABC wherein at least one of theblocks in the block copolymer is an adsorbing segment, and wherein atleast one of the blocks in the block copolymer is a stabilizing segment.9. The inkjet ink set of claim 8, further comprising a cyan ink, amagenta ink and a yellow ink.
 10. The inkjet ink set of claim 8, furthercomprising a black ink.
 11. An inkjet ink set comprising a plurality ofcolored, pigmented inks, at least one of which is a first aqueous inkjetink comprising a vehicle to which has been added an aqueous titaniumdioxide slurry comprising: (a) a titanium dioxide pigment; and (b) acombination of dispersants comprising: (1) a graft copolymer having aweight average molecular weight of from about 4000 to about 100000,comprising from about 90% to about 50% by weight of a polymericbackbone, and from about 10% to about 50% by weight of macromonomer sidechains attached to the backbone, the polymeric backbone and macromonomerside chains comprising 100 wt % of the graft copolymer, wherein: (i) thepolymeric backbone is hydrophobic in comparison to the macromonomer sidechains and comprises polymerized ethylenically unsaturated hydrophobicmonomers and, optionally, up to about 20% by weight, based on the weightof the graft copolymer, of polymerized ethylenically unsaturated acidmonomers; and (ii) each of the macromonomer side chains individually isa hydrophilic polymer containing acids groups attached to the polymericbackbone at a single terminal point, and (A) has a weight averagemolecular weight of from about 1000 to about 30000, and (B) comprisesfrom about 2% to about 100% by weight, based on the weight of themacromonomer side chain, of a polymerized ethylenically unsaturated acidmonomer, and (C) wherein the acid groups are at least partiallyneutralized with an inorganic base or an amine; (2) a block copolymer oftype AB, ABA or ABC wherein at least one of the blocks in the blockcopolymer is an adsorbing segment, and wherein at least one of theblocks in the block copolymer is a stabilizing segment; and (c) a liquidcarrier.
 12. The inkjet ink set of claim 11, further comprising a cyanink, a magenta ink and a yellow ink.
 13. The inkjet ink set of claim 11,further comprising a black ink.
 14. A method for inkjet printing onto asubstrate, comprising the steps of: (1) providing an inkjet printer thatis responsive to digital data signals; (2) loading the printer with asubstrate to be printed; (3) loading the printer with an inkjet ink; and(4) printing onto the substrate using the inkjet ink set in response tothe digital data signals, wherein the inkjet ink is a first aqueousinkjet ink comprising an aqueous vehicle having dispersed therein: (a) atitanium dioxide pigment; (b) a combination of dispersants comprising:(1) a graft copolymer having a weight average molecular weight of fromabout 4000 to about 100000, comprising from about 90% to about 50% byweight of a polymeric backbone, and from about 10% to about 50% byweight of macromonomer side chains attached to the backbone, thepolymeric backbone and macromonomer side chains comprising 100 wt % ofthe graft copolymer, wherein: (i) the polymeric backbone is hydrophobicin comparison to the macromonomer side chains and comprises one or morepolymerized ethylenically unsaturated hydrophobic monomers and,optionally, up to about 20% by weight, based on the weight of the graftcopolymer, of polymerized ethylenically unsaturated acid monomers; and(ii) each of the macromonomer side chains individually is a hydrophilicpolymer containing acids groups attached to the polymeric backbone at asingle terminal point, and (A) has a weight average molecular weight offrom about 1000 to about 30000, and (B) comprises from about 2% to about100% by weight, based on the weight of the macromonomer side chain, of apolymerized ethylenically unsaturated acid monomer, and (C) wherein theacid groups are at least partially neutralized, preferably with aninorganic base and/or an amine; (2) a block copolymer of type AB, ABA orABC wherein at least one of the blocks in the block copolymer is anadsorbing segment, and wherein at least one of the blocks in the blockcopolymer is a stabilizing segment.
 15. A method for inkjet printingonto a substrate, comprising the steps of: (1) providing an inkjetprinter that is responsive to digital data signals; (2) loading theprinter with a substrate to be printed; (3) loading the printer with aninkjet ink; and (4) printing onto the substrate using the inkjet ink setin response to the digital data signals, wherein the inkjet ink is afirst aqueous inkjet ink comprising a vehicle to which has been added anaqueous titanium dioxide slurry comprising: (a) a titanium dioxidepigment; and (b) a combination of dispersants comprising: (1) a graftcopolymer having a weight average molecular weight of from about 4000 toabout 100000, comprising from about 90% to about 50% by weight of apolymeric backbone, and from about 10% to about 50% by weight ofmacromonomer side chains attached to the backbone, the polymericbackbone and macromonomer side chains comprising 100 wt % of the graftcopolymer, wherein: (i) the polymeric backbone is hydrophobic incomparison to the macromonomer side chains and comprises polymerizedethylenically unsaturated hydrophobic monomers and, optionally, up toabout 20% by weight, based on the weight of the graft copolymer, ofpolymerized ethylenically unsaturated acid monomers; and (ii) each ofthe macromonomer side chains individually is a hydrophilic polymercontaining acids groups attached to the polymeric backbone at a singleterminal point, and (A) has a weight average molecular weight of fromabout 1000 to about 30000, and (B) comprises from about 2% to about 100%by weight, based on the weight of the macromonomer side chain, of apolymerized ethylenically unsaturated acid monomer, and (C) wherein theacid groups are at least partially neutralized with an inorganic base oran amine; (2) a block copolymer of type AB, ABA or ABC wherein at leastone of the blocks in the block copolymer is an adsorbing segment, andwherein at least one of the blocks in the block copolymer is astabilizing segment; and (c) a liquid carrier.